Semiconductor Device And Manufacturing Method Thereof

ABSTRACT

A semiconductor device includes an oxide semiconductor layer, a source electrode and a drain electrode electrically connected to the oxide semiconductor layer, a gate insulating layer covering the oxide semiconductor layer, the source electrode, and the drain electrode, and a gate electrode over the gate insulating layer. The source electrode and the drain electrode include an oxide region formed by oxidizing a side surface thereof. Note that the oxide region of the source electrode and the drain electrode is preferably formed by plasma treatment with a high frequency power of 300 MHz to 300 GHz and a mixed gas of oxygen and argon.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/919,437, filed Mar. 13, 2018, now allowed, which is a continuation ofU.S. application Ser. No. 14/974,627, filed Dec. 18, 2015, now U.S. Pat.No. 10,056,494, which is a continuation of U.S. application Ser. No.14/287,320, filed May 27, 2014, now U.S. Pat. No. 9,219,162, which is acontinuation of U.S. application Ser. No. 13/770,022, filed Feb. 19,2013, now U.S. Pat. No. 8,742,544, which is a continuation of U.S.application Ser. No. 12/945,243, filed Nov. 12, 2010, now U.S. Pat. No.8,410,002, which claims the benefit of a foreign priority applicationfiled in Japan as Serial No. 2009-260368 on Nov. 13, 2009, all of whichare incorporated by reference.

TECHNICAL FIELD

A technical field of the present invention relates to a semiconductordevice and a manufacturing method of the semiconductor device. Note thatsemiconductor devices herein refer to general elements and devices whichfunction by utilizing semiconductor characteristics.

BACKGROUND ART

There are a wide variety of metal oxides and such material oxides areused for various applications. Indium oxide is a well-known material andis used as a material for transparent electrodes which are needed forliquid crystal display devices or the like.

Some metal oxides have semiconductor characteristics. Examples of suchmetal oxides having semiconductor characteristics include tungstenoxide, tin oxide, indium oxide, zinc oxide, and the like. A thin filmtransistor in which a channel formation region is formed using such ametal oxide is already known (see, for example, Patent Documents 1 to 4,Non-Patent Document 1, and the like).

Meanwhile, multi-component oxides are also known as metal oxides. Forexample, InGaO₃(ZnO)_(m) (m: natural number) having a homologous phaseis known as a multi-component oxide semiconductor including In, Ga, andZn (see, for example, Non-Patent Documents 2 to 4 and the like).

Furthermore, it is confirmed that an oxide semiconductor including suchan In—Ga—Zn-based oxide can also be applied to a channel formationregion of a thin film transistor (see, for example, Patent Document 5,Non-Patent Documents 5 and 6, and the like).

REFERENCES Patent Documents

-   [Patent Document 1] Japanese Published Patent Application No.    S60-198861-   [Patent Document 2] Japanese Published Patent Application No.    H8-264794-   [Patent Document 3] Japanese Translation of PCT International    Application No. H11-505377-   [Patent Document 4] Japanese Published Patent Application No.    2000-150900-   [Patent Document 5] Japanese Published Patent Application No.    2004-103957

Non-Patent Documents

-   [Non-Patent Document 1] M. W. Prins, K. O. Grosse-Holz, G.    Muller, J. F. M. Cillessen, J. B. Giesbers, R. P. Weening, and R. M.    Wolf, “A ferroelectric transparent thin-film transistor”, Appl.    Phys. Lett., 17 Jun. 1996, Vol. 68, pp. 3650-3652-   [Non-Patent Document 2] M. Nakamura, N. Kimizuka, and T. Mohri, “The    Phase Relations in the In₂O₃—Ga₂ZnO₄—ZnO System at 1350° C.”, J.    Solid State Chem., 1991, Vol. 93, pp. 298-315-   [Non-Patent Document 3] N. Kimizuka, M. Isobe, and M. Nakamura,    “Syntheses and Single-Crystal Data of Homologous Compounds,    In₂O₃(ZnO)_(m) (m=3, 4, and 5), InGaO₃(ZnO)₃, and Ga₂O₃(ZnO). (m=7,    8, 9, and 16) in the In₂O₃—ZnGa₂O₄—ZnO System”, J. Solid State    Chem., 1995, Vol. 116, pp. 170-178-   [Non-Patent Document 4] M. Nakamura, N. Kimizuka, T. Mohri, and M.    Isobe, “Syntheses and crystal structures of new homologous    compounds, indium iron zinc oxides (InFeO₃(ZnO)_(m)) (m: natural    number) and related compounds”, KOTAI BUTSURI (SOLID STATE PHYSICS),    1993, Vol. 28, No. 5, pp. 317-327-   [Non-Patent Document 5] K. Nomura, H. Ohta, K. Ueda, T. Kamiya, M.    Hirano, and H. Hosono, “Thin-film transistor fabricated in    single-crystalline transparent oxide semiconductor”, SCIENCE, 2003,    Vol. 300, pp. 1269-1272-   [Non-Patent Document 6] K. Nomura, H. Ohta, A. Takagi, T. Kamiya, M.    Hirano, and H. Hosono, “Room-temperature fabrication of transparent    flexible thin-film transistors using amorphous oxide    semiconductors”, NATURE, 2004, Vol. 432, pp. 488-492

DISCLOSURE OF INVENTION

It can hardly be said that a transistor including a conventional oxidesemiconductor has characteristics sufficient for practical use, andtransistor characteristics such as subthreshold swing (S value), on/offratio, and reliability need to be improved.

In view of this, it is an object of an embodiment of the disclosedinvention to provide a semiconductor device with a novel structure andfavorable characteristics.

Alternatively, it is an object to provide a manufacturing method of thesemiconductor device with a novel structure.

With respect to a transistor including an oxide semiconductor accordingto one embodiment of the present invention, which has a source electrodeand a drain electrode with an oxidized side surface, characteristicssuch as subthreshold swing (S value), on/off ratio, and reliability aresignificantly improved. Specifically, the following structure can beemployed, for example.

An embodiment of the present invention is a semiconductor deviceincluding an oxide semiconductor layer, a source electrode and a drainelectrode electrically connected to the oxide semiconductor layer, agate insulating layer covering the oxide semiconductor layer, the sourceelectrode, and the drain electrode, and a gate electrode over the gateinsulating layer. The source electrode and the drain electrode have anoxide region formed by oxidizing a side surface thereof. Note that theoxide region is formed while oxygen is supplied to the oxidesemiconductor layer.

In the above embodiment, it is preferable that the oxide region of thesource electrode and the drain electrode be formed by plasma treatmentwith a high frequency power of 300 MHz to 300 GHz and a mixed gas ofoxygen and argon. It is also preferable that a protective insulatinglayer having substantially the same planar shape as that of the sourceelectrode and the drain electrode be provided over the source electrodeand the drain electrode. Note that the expression “substantially thesame” or “substantially same” does not necessarily mean being exactlythe same in a strict sense and can mean being considered as the same.For example, a difference made by a single etching process isacceptable.

In the above embodiment, it is also preferable that the hydrogenconcentration of the oxide semiconductor layer be 5×10¹⁹/cm³ or less. Itis also preferable that the off-state current be 1×10⁻¹³ A or less.

An embodiment of the present invention is a manufacturing method of asemiconductor device, which includes the step of forming an oxidesemiconductor layer over a substrate, forming a source electrode and adrain electrode electrically connected to the oxide semiconductor layer,forming a gate insulating layer covering the oxide semiconductor layer,the source electrode, and the drain electrode after oxidizing a sidesurface of the source electrode and the drain electrode, and forming agate electrode over the gate insulating layer. Note that oxygen issupplied to the oxide semiconductor layer when the side surface of thesource electrode and the drain electrode is oxidized.

In the above embodiment, it is preferable that the side surface of thesource electrode and the drain electrode be oxidized by plasma treatmentwith a high frequency power of 300 MHz to 300 GHz and a mixed gas ofoxygen and argon.

In the above embodiment, it is also preferable that a protectiveinsulating layer having substantially the same planar shape as that ofthe source electrode and the drain electrode be formed over the sourceelectrode and the drain electrode.

In the above embodiment, it is also preferable that the off-statecurrent be made 1×10⁻¹³ A or less by making the hydrogen concentrationof the oxide semiconductor layer 5×10¹⁹/cm³ or less.

Note that the term such as “over” or “below” in this specification andthe like does not necessarily mean that a component is placed “directlyon” or “directly under” another component. For example, the expression“a first gate electrode over a gate insulating layer” does not excludethe case where a component is placed between the gate insulating layerand the gate electrode. Moreover, the terms such as “over” and “below”are only used for convenience of description and can include the casewhere the vertical relation of components is reversed, unless otherwisespecified.

In addition, the term such as “electrode” or “wiring” in thisspecification and the like does not limit a function of a component. Forexample, an “electrode” can be used as part of a “wiring”, and the“wiring” can be used as part of the “electrode”. Furthermore, the term“electrode” or “wiring” can include the case where a plurality of“electrodes” or “wirings” is formed in an integrated manner.

Functions of a “source” and a “drain” are sometimes interchanged witheach other when a transistor of opposite polarity is used or when thedirection of current flowing is changed in circuit operation, forexample. Therefore, the terms “source” and “drain” can be used to denotethe drain and the source, respectively, in this specification.

Note that the term “electrically connected” in this specification andthe like includes the case where components are connected through an“object having any electric function”. There is no particular limitationon an “object having any electric function” as long as electric signalscan be transmitted and received between components that are connectedthrough the object.

Examples of an “object having any electric function” are a switchingelement such as a transistor, a resistor, an inductor, a capacitor, andan element with a variety of functions as well as an electrode and awiring.

According to an embodiment of the disclosed invention, characteristicsof a transistor including an oxide semiconductor are further improved bysupplying oxygen to an oxide semiconductor layer. Here, the oxygensupply process brings the result that a side surface of a source ordrain electrode is oxidized in a transistor including an oxidesemiconductor.

By oxidizing a side surface of a source or drain electrode, it ispossible to prevent short circuit between a gate electrode and thesource or drain electrode which may be caused by a reduction inthickness of a gate insulating layer or defective coverage therewith.

By supplying oxygen to an oxide semiconductor layer as described above,a semiconductor device with a novel structure and excellentcharacteristics can be realized.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a cross-sectional view illustrating a semiconductor device.

FIGS. 2A to 2D are cross-sectional views illustrating a manufacturingprocess of a semiconductor device.

FIGS. 3A to 3C are cross-sectional views illustrating a manufacturingprocess of a semiconductor device.

FIG. 4 is a cross-sectional view of a transistor including an oxidesemiconductor.

FIG. 5 is an energy band diagram (schematic diagram) along an A-A′section in FIG. 4.

FIG. 6A is a diagram illustrating a state where a positive voltage(V_(G)>0) is applied to a gate (GE1) and FIG. 6B is a diagramillustrating a state where a negative voltage (V_(G)<0) is applied tothe gate (GE1).

FIG. 7 is a diagram illustrating the relationships between the vacuumlevel and the work function of a metal (ϕ_(M)) and between the vacuumlevel and the electron affinity (χ) of an oxide semiconductor.

FIGS. 8A and 8B are diagrams illustrating energy required for hotcarrier injection in silicon (Si).

FIGS. 9A and 9B are diagrams illustrating energy required for hotcarrier injection in an In—Ga—Zn—O-based oxide semiconductor (IGZO).

FIGS. 10A and 10B are diagrams illustrating energy required for hotcarrier injection in silicon carbide (4H—SiC).

FIG. 11 is a diagram showing the results of device simulation as toshort-channel effect.

FIG. 12 is a diagram showing the results of device simulation as toshort-channel effect.

FIG. 13 is a diagram showing C—V characteristics.

FIG. 14 is a diagram illustrating the relationship between V_(G) and(1/C)².

FIGS. 15A to 15F are cross-sectional views each illustrating asemiconductor device.

FIG. 16 is a diagram illustrating the relationship between the thicknessof an oxide region formed by plasma treatment and the treatment time.

BEST MODE FOR CARRYING OUT THE INVENTION

Examples of embodiments of the present invention will be described belowwith reference to the drawings. Note that the present invention is notlimited to the following description and it will be readily appreciatedby those skilled in the art that the modes and details of the presentinvention can be modified in various ways without departing from thespirit and the scope thereof. Therefore, the present invention shouldnot be construed as being limited to the description in the followingembodiments.

In addition, the position, size, range, or the like of each componentillustrated in drawings and the like is not accurately represented insome cases for easy understanding. Therefore, the disclosed invention isnot necessarily limited to the position, size, range, or the like asdisclosed in the drawings and the like.

Note that ordinal numbers such as “first”, “second”, and “third” in thisspecification and the like are used in order to avoid confusion amongcomponents, and the terms do not limit the components numerically.

Embodiment 1

In this embodiment, a structure and a manufacturing method of asemiconductor device according to one embodiment of the disclosedinvention will be described with reference to FIG. 1, FIGS. 2A to 2D,and FIGS. 3A to 3C.

<Structure of Semiconductor Device>

FIG. 1 is a cross-sectional view illustrating a transistor 150 which isan example of a structure of a semiconductor device. Note that thetransistor 150 is an n-channel transistor here; alternatively, ap-channel transistor may be used.

The transistor 150 includes an oxide semiconductor layer 104 a providedover a substrate 100 with an the insulating layer 102 interposedtherebetween, a source or drain electrode 106 a and a source or drainelectrode 106 b electrically connected to the oxide semiconductor layer104 a, a gate insulating layer 112 covering the source or drainelectrode 106 a and the source or drain electrode 106 b, and a gateelectrode 114 over the gate insulating layer 112 (see FIG. 1).

In addition, an interlayer insulating layer 116 and an interlayerinsulating layer 118 are provided over the transistor 150.

Here, the source or drain electrode 106 a and the source or drainelectrode 106 b each include an oxide region 110 formed by oxidizing aside surface thereof. With the oxide region 110, it is possible toprevent short circuit between the gate electrode and the source or drainelectrode which may be caused by a reduction in thickness of the gateinsulating layer or defective coverage therewith.

In addition, the oxide semiconductor layer 104 a is preferably an oxidesemiconductor layer which is purified by sufficiently removing animpurity such as hydrogen therefrom and supplying oxygen thereto.Specifically, the hydrogen concentration of the oxide semiconductorlayer 104 a is 5×10¹⁹/cm³ or less, preferably 5×10¹⁸/cm³ or less, morepreferably 5×10¹⁷/cm³ or less. Note that the oxide semiconductor layer104 a which is purified by sufficiently reducing hydrogen concentrationand supplying oxygen has a carrier concentration (e.g., less than1×10¹²/cm³, preferably 1×10¹¹/cm³ or less) which is sufficiently lowerthan that of a general silicon wafer (a silicon wafer to which animpurity element such as phosphorus or boron is slightly added)(approximately 1×10¹⁴/cm³). The transistor 150 with excellent off-statecurrent characteristics can be obtained with the use of such an i-typeor substantially i-type oxide semiconductor. For example, when the drainvoltage V_(D) is +1 V or +10 V and the gate voltage V_(G) is set in therange of from −20 V to −5 V, the off-state current is 1×10⁻¹³ A or less.Note that the above hydrogen concentration of the oxide semiconductorlayer 104 a is measured by secondary ion mass spectrometry (SIMS).

Note that an oxide semiconductor included in the oxide semiconductorlayer is not particularly limited as long as it has a non-single-crystalstructure. A variety of structures, such as an amorphous structure, amicrocrystalline (nanocrystalline or the like) structure, apolycrystalline structure, a structure in which microcrystals orpolycrysrtals are included in an amorphous material, or a structure inwhich microcrystals or polycrystals are formed at a surface of anamorphous structure, can be employed.

<Manufacturing Method of Semiconductor Device>

Next, a manufacturing method of the transistor 150 will be describedwith reference to FIGS. 2A to 2D and FIGS. 3A to 3C.

First, the insulating layer 102 is formed over the substrate 100. Then,an oxide semiconductor layer 104 is formed over the insulating layer 102(see FIG. 2A).

The substrate 100 may be any substrate that has an insulating surfaceand may be, for example, a glass substrate. The glass substrate ispreferably a non-alkali glass substrate. As a material of the non-alkaliglass substrate, a glass material such as aluminosilicate glass,aluminoborosilicate glass, barium borosilicate glass, or the like isused, for example. Alternatively, as the substrate 100, an insulatingsubstrate formed using an insulator such as a ceramic substrate, aquartz substrate, or a sapphire substrate, a semiconductor substratewhich is formed using a semiconductor material such as silicon and whosesurface is covered with an insulating material, or a conductivesubstrate which is formed using a conductor such as metal or stainlesssteel and whose surface is covered with an insulating material can beused. A plastic substrate can also be used as long as it can withstandheat treatment in a manufacturing process.

The insulating layer 102 functions as a base and can be formed by a CVDmethod, a sputtering method, or the like. The insulating layer 102 ispreferably formed so as to include silicon oxide, silicon nitride,silicon oxynitride, silicon nitride oxide, aluminum oxide, hafniumoxide, tantalum oxide, or the like. Note that the insulating layer 102may have a single-layer structure or a layered structure. There is noparticular limitation on the thickness of the insulating layer 102; theinsulating layer 102 can have a thickness of 10 nm to 500 nm, forexample. Here, the insulating layer 102 is not an essential component;therefore, a structure in which the insulating layer 102 is not providedis also possible.

If hydrogen, water, or the like is contained in the insulating layer102, hydrogen may enter the oxide semiconductor layer or extract oxygenfrom the oxide semiconductor layer, whereby characteristics of thetransistor may be degraded. Therefore, it is desirable to form theinsulating layer 102 so as to include as little hydrogen or water aspossible.

In the case of using a sputtering method or the like, for example, it isdesirable that the insulating layer 102 be formed in a state wheremoisture remaining in the treatment chamber is removed. In order toremove moisture remaining in the treatment chamber, an entrapment vacuumpump such as a cryopump, an ion pump, or a titanium sublimation pump ispreferably used. A turbo pump provided with a cold trap may be used.From the treatment chamber evacuated with a cryopump or the like,hydrogen, water, or the like is sufficiently removed; thus, theconcentration of an impurity in the insulating layer 102 can be reduced.

When the insulating layer 102 is formed, it is desirable to use ahigh-purity gas in which an impurity such as hydrogen or water isreduced so that the concentration is decreased to approximately a valueexpressed in the unit “ppm” (preferably, “ppb”).

As the oxide semiconductor layer 104, an oxide semiconductor layerformed using any of the following materials can be applied:four-component metal oxide such as In—Sn—Ga—Zn—O; three-component metaloxide such as In—Ga—Zn—O, In—Sn—Zn—O, In—Al—Zn—O, Sn—Ga—Zn—O,Al—Ga—Zn—O, and Sn—Al—Zn—O; two-component metal oxide such as In—Zn—O,Sn—Zn—O, Al—Zn—O, Zn—Mg—O, Sn—Mg—O, and In—Mg—O; In—O; Sn—O; and Zn—O.In addition, the above oxide semiconductor layer may include SiO₂.

As the oxide semiconductor layer 104, a thin film including a materialrepresented by InMO₃(ZnO)_(m) (m>0) can be used. Here, M represents oneor more metal elements selected from Ga, Al, Mn, and Co. For example, Mcan be Ga, Ga and Al, Ga and Mn, Ga and Co, or the like. An oxidesemiconductor material which is represented by InMO₃(ZnO)_(m) (m>0) andincludes Ga as M may be referred to as an In—Ga—Zn—O oxidesemiconductor, and a thin film of the In—Ga—Zn—O oxide semiconductor maybe referred to as an In—Ga—Zn—O oxide semiconductor film (an In—Ga—Zn—Oamorphous film) or the like.

In this embodiment, as the oxide semiconductor layer 104, an amorphousoxide semiconductor layer is formed by a sputtering method using atarget for depositing an In—Ga—Zn—O-based oxide semiconductor. Note thatsince crystallization of an amorphous oxide semiconductor layer can besuppressed by adding silicon to the amorphous oxide semiconductor layer,the oxide semiconductor layer 104 may be formed, for example, using atarget including SiO₂ of 2 wt % to 10 wt %.

As a target used for forming the oxide semiconductor layer 104 by asputtering method, a metal oxide target containing zinc oxide as itsmain component can be used, for example. Moreover, a target fordepositing an oxide semiconductor including In, Ga, and Zn (acomposition ratio of In₂O₃:Ga₂O₃:ZnO=1:1:1 [molar ratio] orIn:Ga:Zn=1:1:0.5 [atomic ratio]), or the like can be used, for example.Furthermore, a target for depositing an oxide semiconductor includingIn, Ga, and Zn (having a composition ratio of In:Ga:Zn=1:1:1 [atomicratio] or a composition ratio of In:Ga:Zn=1:1:2 [atomic ratio]) may beused. The filling rate of a target for depositing an oxide semiconductoris 90% to 100%, preferably 95% or higher (e.g., 99.9%). The oxidesemiconductor layer 104 which is dense is formed using a target fordepositing an oxide semiconductor with a high filling rate.

The atmosphere in which the oxide semiconductor layer 104 is formed ispreferably a rare gas (typically, argon) atmosphere, an oxygenatmosphere, or a mixed atmosphere of a rare gas (typically, argon) andoxygen. Specifically, it is preferable to use a high-purity gasatmosphere, for example, from which an impurity such as hydrogen, water,a hydroxyl group, or hydride is removed so that the concentration isdecreased to approximately a value expressed in the unit “ppm”(preferably, “ppb”).

In forming the oxide semiconductor layer 104, the substrate is held in atreatment chamber that is maintained under reduced pressure, and thesubstrate is heated to a temperature of 100° C. to 600° C., preferably200° C. to 400° C. Then, a sputtering gas from which hydrogen and waterare removed is introduced into the treatment chamber from whichremaining moisture is removed, and the oxide semiconductor layer 104 isformed using metal oxide as a target. By forming the oxide semiconductorlayer 104 while heating the substrate, the concentration of an impurityin the oxide semiconductor layer 104 can be decreased. Moreover, damagedue to sputtering is reduced. In order to remove moisture remaining inthe treatment chamber, an entrapment vacuum pump is preferably used. Forexample, a cryopump, an ion pump, a titanium sublimation pump, or thelike can be used. A turbo pump provided with a cold trap may be used.From the treatment chamber evacuated with a cryopump or the like,hydrogen, water, or the like is sufficiently removed; thus, theconcentration of an impurity in the oxide semiconductor layer 104 can bereduced.

For example, the conditions for forming the oxide semiconductor layer104 can be as follows: the distance between the substrate and the targetis 100 mm, the pressure is 0.6 Pa, the direct current (DC) power is 0.5kW, and the atmosphere is an oxygen atmosphere (the proportion of theoxygen flow is 100%). Note that a pulsed direct current (DC) powersource is preferably used because powder substances (also referred to asparticles or dust) generated in film formation can be reduced and thefilm thickness can be uniform. The thickness of the oxide semiconductorlayer is set in the range of 2 nm to 200 nm, preferably 5 nm to 30 nm.Note that the appropriate thickness of the oxide semiconductor layer 104differs depending on the oxide semiconductor material to be used, theintended use, or the like; therefore, the thickness may be determined asappropriate in accordance with the material, the intended use, or thelike.

Note that before the oxide semiconductor layer 104 is formed by asputtering method, reverse sputtering in which plasma is generated withan argon gas introduced is preferably performed so that a materialattached to the surface of the insulating layer 102 is removed. Here,the reverse sputtering is a method by which ions collide with a surfaceto be processed so that the surface is modified, in contrast to normalsputtering by which ions collide with a sputtering target. An example ofa method for making ions collide with a surface to be processed is amethod in which high-frequency voltage is applied to the surface in anargon atmosphere so that plasma is generated near a substrate. Note thatan atmosphere of nitrogen, helium, oxygen, or the like may be usedinstead of an argon atmosphere.

Next, the oxide semiconductor layer 104 is processed by a method such asetching using a mask; thus, the oxide semiconductor layer 104 a havingan island shape is formed (see FIG. 2B).

As a method for etching the oxide semiconductor layer 104, either dryetching or wet etching may be employed. It is needless to say that dryetching and wet etching can be used in combination. The etchingconditions (e.g., an etching gas or an etchant, etching time, andtemperature) are set as appropriate depending on the material so thatthe oxide semiconductor layer 104 can be etched into a desired shape.

As the dry etching method, a parallel plate reactive ion etching (RIE)method, an inductively coupled plasma (ICP) etching method, or the likecan be used. Also in this case, etching conditions (e.g., the amount ofelectric power applied to a coiled electrode, the amount of electricpower applied to an electrode on the substrate side, and the electrodetemperature on the substrate side) need to be set as appropriate.

An example of an etching gas which can be used for dry etching is a gascontaining chlorine (a chlorine-based gas such as chlorine (Cl₂), boronchloride (BCl₃), silicon tetrachloride (SiCl₄), or carbon tetrachloride(CCl₄)). Moreover, a gas containing fluorine (a fluorine-based gas suchas carbon tetrafluoride (CF₄), sulfur fluoride (SF₆), nitrogen fluoride(NF₃), or trifluoromethane (CHF₃)), hydrogen bromide (HBr), oxygen (O₂),any of these gases to which a rare gas such as helium (He) or argon (Ar)is added, or the like may be used.

An example of an etchant which can be used for wet etching includes amixed solution of phosphoric acid, acetic acid, and nitric acid, anammonia-hydrogen peroxide mixture (hydrogen peroxide solution of 31 wt%: ammonia solution of 28 wt %: water=5:2:2), or the like. An etchantsuch as ITO-07N (produced by KANTO CHEMICAL CO., INC.) may also be used.

After that, first heat treatment is preferably performed on the oxidesemiconductor layer 104 a. Water (including a hydroxyl group), hydrogen,or the like contained in the oxide semiconductor layer 104 a can beremoved by the first heat treatment. The temperature of the first heattreatment is set in the range of 300° C. to 750° C., preferably 400° C.to 700° C. For example, the substrate 100 is introduced into an electricfurnace including a resistance heating element or the like, and theoxide semiconductor layer 104 a is subjected to heat treatment at 450°C. for one hour in a nitrogen atmosphere. The oxide semiconductor layer104 a is not exposed to the air during the heat treatment so that entryof water or hydrogen can be prevented.

The heat treatment apparatus is not limited to the electric furnace andcan be an apparatus for heating an object to be processed by thermalradiation or thermal conduction from a medium such as a heated gas. Forexample, a rapid thermal annealing (RTA) apparatus such as a gas rapidthermal annealing (GRTA) apparatus or a lamp rapid thermal annealing(LRTA) apparatus can be used. An LRTA apparatus is an apparatus forheating an object to be processed by radiation of light (anelectromagnetic wave) emitted from a lamp such as a halogen lamp, ametal halide lamp, a xenon arc lamp, a carbon arc lamp, a high pressuresodium lamp, or a high pressure mercury lamp. A GRTA apparatus is anapparatus for performing heat treatment using a high-temperature gas. Asthe gas, an inert gas that does not react with an object by heattreatment, for example, nitrogen or a rare gas such as argon is used.

For example, as the first heat treatment, a GRTA process may beperformed as follows. The substrate is put in an inert gas atmospherethat has been heated to a high temperature of 650° C. to 700° C., heatedfor several minutes, and taken out of the inert gas atmosphere. The GRTAprocess enables high-temperature heat treatment in a short time.Moreover, the GRTA process can be employed even when the temperatureexceeds the upper temperature limit of the substrate because the heattreatment can be achieved in a short time. In the case where a glasssubstrate is used, shrinkage of the substrate becomes a problem at atemperature higher than the upper temperature limit (strain point) butdoes not in the case of performing heat treatment in a short time. Notethat the inert gas may be switched to a gas including oxygen during theprocess. This is because defects caused by oxygen deficiency can bereduced by performing the first heat treatment in an atmosphereincluding oxygen.

Note that as the inert gas atmosphere, an atmosphere that containsnitrogen or a rare gas (e.g., helium, neon, or argon) as its maincomponent and does not contain water, hydrogen, or the like ispreferably used. For example, the purity of nitrogen or a rare gas suchas helium, neon, or argon introduced into a heat treatment apparatus isset to 6 N (99.9999%) or more, preferably 7 N (99.99999%) or more (i.e.,the impurity concentration is 1 ppm or less, preferably 0.1 ppm orless).

Depending on the conditions of the first heat treatment or the materialincluded in the oxide semiconductor layer, the oxide semiconductor layeris sometimes crystallized to be microcrystalline or polycrystalline. Forexample, the oxide semiconductor layer sometimes becomes amicrocrystalline oxide semiconductor layer having a degree ofcrystallization of 90% or more, or 80% or more. Further, depending onthe conditions of the first heat treatment or the material of the oxidesemiconductor layer, the oxide semiconductor layer may be an amorphousoxide semiconductor layer containing no crystalline component.

Furthermore, in the oxide semiconductor layer, microcrystals (the grainsize is 1 nm to 20 nm, typically 2 nm to 4 nm) are sometimes mixed in anamorphous oxide semiconductor (e.g., at a surface of the oxidesemiconductor layer). The electrical characteristics of the oxidesemiconductor layer can also be changed by mixing and aligningmicrocrystals in an amorphous semiconductor in the above manner.

For example, when the oxide semiconductor layer is formed using a targetfor depositing an In—Ga—Zn—O-based oxide semiconductor, the electricalcharacteristics of the oxide semiconductor layer can be changed byformation of a microcrystalline region in which crystal grains ofIn₂Ga₂ZnO₇ with electrical anisotropy are aligned. The microcrystallineregion is preferably a region in which the crystal grains are arrangedso that the c-axis of In₂Ga₂ZnO₇ is perpendicular to a surface of theoxide semiconductor layer, for example. By forming a region in whichcrystal grains are arranged in such a manner, the conductivity in thedirection parallel to the surface of the oxide semiconductor layer canbe improved and insulating properties in the direction perpendicular tothe surface of the oxide semiconductor layer can be improved.Furthermore, such a microcrystalline region functions to suppress entryof an impurity such as water or hydrogen into the oxide semiconductorlayer.

Note that the oxide semiconductor layer including the microcrystallineregion can be formed by heating the surface of the oxide semiconductorlayer by a GRTA process. Further, the oxide semiconductor layer can beformed in a more preferred manner by using a sputtering target in whichthe amount of Zn is smaller than that of In or Ga.

The first heat treatment of the oxide semiconductor layer 104 a can beperformed on the oxide semiconductor layer that has not yet beenprocessed into the oxide semiconductor layer 104 a having an islandshape. In that case, after the first heat treatment, the substrate 100is taken out of the heating apparatus and a photolithography step isperformed.

Note that the first heat treatment can also be referred to asdehydration treatment, dehydrogenation treatment, or the like. Thedehydration treatment or dehydrogenation treatment can be performedafter the oxide semiconductor layer is formed and, for example, after asource electrode and a drain electrode are stacked over the oxidesemiconductor layer 104 a or after a gate insulating layer is formedover the source electrode and the drain electrode. Such dehydrationtreatment or dehydrogenation treatment may be performed once or pluraltimes.

Next, a conductive layer 106 is formed so as to be in contact with theoxide semiconductor layer 104 a and then an insulating layer 108 isformed over the conductive layer 106 (see FIG. 3C). Note that theinsulating layer 108 is not an essential component but is effective inselectively oxidizing a side surface of a source electrode and a drainelectrode to be formed later.

The conductive layer 106 can be formed by a PVD method such as asputtering method, or a CVD method such as a plasma CVD method. Theconductive layer 106 can be formed using an element selected fromaluminum, chromium, copper, tantalum, titanium, molybdenum, andtungsten, an alloy including any of these elements as a component, orthe like. A material including one or more of manganese, magnesium,zirconium, beryllium, and thorium may be used. A material includingaluminum and one or more of elements selected from titanium, tantalum,tungsten, molybdenum, chromium, neodymium, and scandium may be used.

The conductive layer 106 may also be formed using a conductive metaloxide. As the conductive metal oxide, indium oxide (In₂O₃), tin oxide(SnO₂), zinc oxide (ZnO), an indium oxide-tin oxide alloy (In₂O₃—SnO₂,which is abbreviated to ITO in some cases), an indium oxide-zinc oxidealloy (In₂O₃—ZnO), or any of these metal oxide materials in whichsilicon or silicon oxide is included can be used.

The conductive layer 106 may have a single-layer structure or a layeredstructure including two or more layers. For example, the conductivelayer 142 may have a single-layer structure of an aluminum filmincluding silicon, a two-layer structure in which a titanium film isstacked over an aluminum film, or a three-layer structure in which atitanium film, an aluminum film, and a titanium film are stacked in thisorder. Here, a three-layer structure of a titanium film, an aluminumfilm, and a titanium film is employed.

Note that an oxide conductive layer may be formed between the oxidesemiconductor layer 104 a and the conductive layer 106. The oxideconductive layer and the conductive layer 106 can be formed successively(successive formation). With such an oxide conductive layer, theresistance of a source region or a drain region can be lowered, whichmakes it possible to achieve high-speed operation of the transistor.

The insulating layer 108 can be formed by a CVD method, a sputteringmethod, or the like. The insulating layer 108 is preferably formed so asto include silicon oxide, silicon nitride, silicon oxynitride, siliconnitride oxide, aluminum oxide, hafnium oxide, tantalum oxide, or thelike. Note that the insulating layer 108 may have a single-layerstructure or a layered structure. There is no particular limitation onthe thickness of the insulating layer 108; the insulating layer 108 canhave a thickness of 10 nm to 500 nm, for example.

Next, the conductive layer 106 and the insulating layer 108 areselectively etched; thus, the source or drain electrode 106 a, thesource or drain electrode 106 b, an insulating layer 108 a, and aninsulating layer 108 b are formed. Then, oxidation treatment isperformed in order to supply oxygen to the oxide semiconductor layer 104a. By the oxidation treatment, the oxide regions 110 are formed in partof the source or drain electrode 106 a and the source or drain electrode106 b (see FIG. 2D). In addition, as indicated by a dotted line, aregion supplied with oxygen is formed in the oxide semiconductor layer104 a. Note that the range of the region supplied with oxygen changesvariously depending on the material included in the oxide semiconductorlayer 104 a, the conditions of the oxidation treatment, or the like. Forexample, oxygen can also be supplied to the lower interface of the oxidesemiconductor layer 104 a.

For light exposure in forming a mask used for etching, ultravioletlight, KrF laser light, or ArF laser light is preferably used.Particularly for light exposure in the case where the channel length (L)is less than 25 nm, light exposure for forming a mask is preferablyperformed with extreme ultraviolet light whose wavelength is severalnanometers to several tens of nanometers, which is extremely short. Inlight exposure using extreme ultraviolet light, resolution is high anddepth of focus is large. Therefore, the channel length of a transistor,which is formed later, can also be 10 nm to 1000 nm. By a decrease inchannel length by such a method, operation speed can be improved. Inaddition, the off-state current of a transistor including theabove-described oxide semiconductor is small; thus, an increase in powerconsumption due to miniaturization can be suppressed.

The materials and etching conditions of the conductive layer 106 and theoxide semiconductor layer 104 a are adjusted as appropriate so that theoxide semiconductor layer 104 a is not removed in etching of theconductive layer 106. Note that in some cases, the oxide semiconductorlayer 104 a is partly etched in the etching step and thus has a grooveportion (a recessed portion) depending on the materials and the etchingconditions.

In order to reduce the number of masks to be used and reduce the numberof steps, an etching step may be performed with the use of a resist maskformed using a multi-tone mask which is a light-exposure mask throughwhich light is transmitted to have a plurality of intensities. A resistmask formed with the use of a multi-tone mask has a plurality ofthicknesses (has a stair-like shape) and further can be changed in shapeby ashing; therefore, the resist mask can be used in a plurality ofetching steps. That is, a resist mask corresponding to at least twokinds of different patterns can be formed by using one multi-tone mask.Thus, the number of light-exposure masks can be reduced and the numberof corresponding photolithography steps can also be reduced, whereby aprocess can be simplified.

The oxidation treatment is preferably performed using oxygen plasmaexcited with a microwave (300 MHz to 300 GHz), which may be referred toas plasma oxidation treatment. The reason is that high-density plasma isrealized by plasma excitation with a microwave and damage to the oxidesemiconductor layer 104 a can be sufficiently reduced.

Specifically, the above treatment can be performed, for example, at afrequency of 300 MHz to 300 GHz (typically, 2.45 GHz) under a pressureof 50 Pa to 5000 Pa (typically, 500 Pa) at a substrate temperature of200° C. to 400° C. (typically, 300° C.) with the use of a mixed gas ofoxygen and argon.

By the above oxidation treatment, oxygen is supplied to the oxidesemiconductor layer 104 a. Therefore, damage to the oxide semiconductorlayer 104 a can be sufficiently reduced, and in addition, localizedstates due to oxygen deficiency can be reduced. In other words,characteristics of the oxide semiconductor layer 104 a can be furtherimproved.

Note that without limitation to the plasma oxidation treatment with amicrowave, any other method that enables a sufficient reduction indamage to the oxide semiconductor layer 104 a and a supply of oxygen tothe oxide semiconductor layer 104 a can be used. For example, a methodsuch as heat treatment in an atmosphere including oxygen can be used.

In combination with the oxidation treatment, treatment for removingwater, hydrogen, or the like from the oxide semiconductor layer 104 amay be performed. For example, plasma treatment using a gas such asnitrogen or argon can be performed.

Note that by the oxidation treatment, the oxide regions 110 are formedin part of the source or drain electrode 106 a and the source or drainelectrode 106 b (particularly, portions corresponding to side surfacesthereof). The oxide regions 110 are effective particularly when thetransistor 150 is miniaturized (for example, when the channel length isshorter than 1000 nm). With the miniaturization of the transistor, thegate insulating layer needs to have a smaller thickness. The reason whythe oxide regions 110 are provided is that the oxide regions 110 canprevent short circuit between the gate electrode and the source or drainelectrodes, which may be caused by a reduction in thickness of the gateinsulating layer or defective coverage therewith. Note that the oxideregions 110 are sufficiently effective when having a thickness of 5 nmor more (preferably, 10 nm or more).

The oxidation treatment is also effective in terms of improvement infilm quality of an exposed portion of the insulating layer 102.

Note that the insulating layer 108 a and the insulating layer 108 b areimportant in that these insulating layers function to prevent oxidationof upper portions of the source or drain electrode 106 a and the sourceor drain electrode 106 b. This is because it is significantly difficultto perform the plasma treatment while the mask used for etching remains.

Although FIG. 2D illustrates the case where the source or drainelectrode 106 a, the source or drain electrode 106 b, the insulatinglayer 108 a, and the insulating layer 108 b are formed at a time byselectively etching the conductive layer 106 and the insulating layer108 illustrated in FIG. 2C, an embodiment of the disclosed invention isnot limited to this example.

For example, the source or drain electrode 106 a, the source or drainelectrode 106 b, the insulating layer 108 a, and the insulating layer108 b may be completed as follows: an opening that reaches the channelformation region of the transistor is formed by selective etching ofonly a region of the conductive layer 106 and the insulating layer 108which overlaps the oxide semiconductor layer 104 a; then, the region issubjected to the plasma treatment so that oxygen is supplied to theoxide semiconductor layer 104 a and the exposed portion of theconductive layer 106 is oxidized; then, etching is performed again. Inthe case of employing such steps, oxidation treatment can be performedon only an intended portion. Therefore, there is an advantage that theother portion can be prevented from being adversely affected by theoxidation treatment.

Next, the gate insulating layer 112 is formed in contact with part ofthe oxide semiconductor layer 104 a without exposure to the air (seeFIG. 3A). The gate insulating layer 112 can be formed by a CVD method, asputtering method, or the like. The gate insulating layer 112 ispreferably formed so as to include silicon oxide, silicon nitride,silicon oxynitride, silicon nitride oxide, aluminum oxide, hafniumoxide, tantalum oxide, or the like. Note that the gate insulating layer112 may have a single-layer structure or a layered structure. There isno particular limitation on the thickness of the gate insulating layer112; the gate insulating layer 112 can have a thickness of 10 nm to 500nm, for example.

Note that an i-type or substantially i-type oxide semiconductor obtainedby removing an impurity (a purified oxide semiconductor) is highlysusceptible to interface states or interface charges; therefore, thegate insulating layer 112 needs to have high quality.

For example, a high-density plasma CVD method using a microwave (e.g.,2.45 GHz) is favorable in that the gate insulating layer 112 can bedense and have high withstand voltage and high quality. This is becausea close contact between a purified oxide semiconductor layer and ahigh-quality gate insulating layer reduces interface states and producesdesirable interface characteristics.

It is needless to say that another method such as a sputtering method ora plasma CVD method can also be employed as long as a high-qualityinsulating layer can be formed as the gate insulating layer 112.Moreover, it is possible to use an insulating layer whose quality,interface characteristics, or the like is improved with heat treatmentperformed after the formation of the insulating layer. In any case, aninsulating layer that has a reduced interface state density and can forma favorable interface with an oxide semiconductor layer, as well ashaving favorable film quality as the gate insulating layer 112, isformed.

By thus improving characteristics of the interface with a gateinsulating layer and eliminating an impurity, particularly hydrogen,water, or the like, from an oxide semiconductor, it is possible toobtain a stable transistor whose threshold voltage (V_(th)) does notchange with a gate bias-temperature stress test (BT test, e.g., at 85°C. and 2×10⁶ V/cm for 12 hours).

After that, second heat treatment is performed in an inert gasatmosphere or an oxygen atmosphere. The temperature of the heattreatment is set in the range of 200° C. to 400° C., preferably 250° C.to 350° C. For example, the heat treatment may be performed at 250° C.for 1 hour in a nitrogen atmosphere. The second heat treatment canreduce variation in electric characteristics of the transistor. Notethat the second heat treatment is performed in this embodiment after thegate insulating layer 112 is formed; there is no particular limitationon the timing of the second heat treatment as long as it is performedafter the first heat treatment.

Next, the gate electrode 114 is formed over the gate insulating layer112 in a region overlapping the oxide semiconductor layer 104 a (seeFIG. 3B). The gate electrode 114 can be formed by forming a conductivelayer over the gate insulating layer 112 and then selectively patterningthe conductive layer.

The conductive layer can be formed by a PVD method such as a sputteringmethod, or a CVD method such as a plasma CVD method. The conductivelayer can be formed using an element selected from aluminum, chromium,copper, tantalum, titanium, molybdenum, and tungsten, an alloy includingany of these elements as a component, or the like. A material includingone or more of manganese, magnesium, zirconium, beryllium, and thoriummay be used. A material including aluminum and one or more of elementsselected from titanium, tantalum, tungsten, molybdenum, chromium,neodymium, and scandium may be used.

The conductive layer may also be formed using a conductive metal oxide.As the conductive metal oxide, indium oxide (In₂O₃), tin oxide (SnO₂),zinc oxide (ZnO), an indium oxide-tin oxide alloy (In₂O₃—SnO₂, which isabbreviated to ITO in some cases), an indium oxide-zinc oxide alloy(In₂O₃—ZnO), or any of these metal oxide materials in which silicon orsilicon oxide is included can be used.

The conductive layer may have a single-layer structure or a layeredstructure including two or more layers. For example, the conductivelayer may have a single-layer structure of an aluminum film includingsilicon, a two-layer structure in which a titanium film is stacked overan aluminum film, or a three-layer structure in which a titanium film,an aluminum film, and a titanium film are stacked in this order. Here,the conductive layer is formed using a material including titanium andthen processed into the gate electrode 114.

Next, the interlayer insulating layer 116 and the interlayer insulatinglayer 118 are formed over the gate insulating layer 112 and the gateelectrode 114 (see FIG. 3C). The interlayer insulating layers 116 and118 can be formed by a PVD method, a CVD method, or the like. Theinterlayer insulating layers 116 and 118 can be formed using a materialincluding an inorganic insulating material such as silicon oxide,silicon nitride oxide, silicon nitride, hafnium oxide, aluminum oxide,or tantalum oxide. Note that a layered structure of the interlayerinsulating layers 116 and 118 is used in this embodiment, but anembodiment of the disclosed invention is not limited to this example. Asingle-layer structure or a layered structure including three or morelayers can also be used.

Note that the interlayer insulating layer 118 is desirably formed so asto have a flat surface. This is because an electrode, a wiring, or thelike can be favorably formed over the interlayer insulating layer 118when the interlayer insulating layer 118 is formed so as to have a flatsurface.

Through the above steps, the transistor 150 including an oxidesemiconductor is completed.

In the case where the transistor 150 is formed by the above-describedmethod, the hydrogen concentration of the oxide semiconductor layer 104a is 5×10¹⁹/cm³ or less and the off-state current of the transistor 162is 1×10⁻¹³ A or less. The transistor 150 with excellent characteristicscan be obtained by the application of the oxide semiconductor layer 104a that is purified by a sufficient reduction in hydrogen concentrationand by a supply of oxygen as described above. Note that it is preferablethat oxygen be supplied shortly after the hydrogen concentration isreduced because there is no possibility that hydrogen, water, or thelike enters the oxide semiconductor layer and thus an oxidesemiconductor layer with extremely favorable characteristics can berealized. It is needless to say that a treatment for reducing thehydrogen concentration and a treatment for supplying oxygen do not needto be performed successively as long as an oxide semiconductor layerwith favorable characteristics can be realized. For example, anothertreatment may be performed between these treatments. Alternatively,these treatments may be performed at the same time.

In this embodiment, oxygen plasma treatment is performed on the oxidesemiconductor layer 104 a in order to supply oxygen to the oxidesemiconductor layer 104 a. Accordingly, the transistor 150 has bettercharacteristics. In addition, a region corresponding to a side surfaceof the source or drain electrode is oxidized; thus, short circuitbetween the gate electrode and the source electrode (or the drainelectrode), which may be caused by a reduction in thickness of the gateinsulating layer, can be prevented.

Note that considerable research has been done on properties of oxidesemiconductors; however, the research does not include the idea ofsufficiently reducing localized states themselves. According to anembodiment of the disclosed invention, a purified oxide semiconductor ismanufactured by removing water and hydrogen, which might be a cause oflocalized states, from the oxide semiconductor. This is based on theidea of sufficiently reducing localized states themselves. Thus,excellent industrial products can be manufactured.

Note that oxygen may be removed while hydrogen, water, or the like isbeing removed. Therefore, it is preferable to realize a purified(i-type) oxide semiconductor in such a manner that oxygen is supplied tometal dangling bonds generated by oxygen deficiency so that thelocalized states due to oxygen deficiency are reduced. For example, anoxygen-excess oxide film is formed in close contact with a channelformation region and heat treatment is performed at a temperature of200° C. to 400° C., typically 250° C., whereby oxygen can be suppliedfrom the oxide film and the localized states due to oxygen deficiencycan be reduced. An inert gas may be switched to a gas including oxygenduring the second heat treatment. Further, after the second heattreatment, oxygen can be supplied to the oxide semiconductor through atemperature decreasing process in an oxygen atmosphere or an atmospherein which hydrogen, water, or the like is sufficiently reduced.

It can be considered that a factor causing deterioration ofcharacteristics of an oxide semiconductor is a shallow level due toexcess hydrogen at 0.1 eV to 0.2 eV below the conduction band, a deeplevel due to oxygen deficiency, or the like. The technical idea thathydrogen is thoroughly eliminated and oxygen is adequately supplied inorder to eliminate such a defect would be right.

An oxide semiconductor is generally considered as an n-typesemiconductor; however, according to an embodiment of the disclosedinvention, an i-type oxide semiconductor is realized by removing animpurity such as water or hydrogen and supplying oxygen which is aconstituent element of the oxide semiconductor. In this respect, it canbe said that an embodiment of the disclosed invention includes a noveltechnical idea because it is not an i-type semiconductor such as siliconwhich is obtained by adding an impurity.

<Electrical Conduction Mechanism of Transistor Including OxideSemiconductor>

An electrical conduction mechanism of a transistor including an oxidesemiconductor will be described with reference to FIG. 4, FIG. 5, FIGS.6A and 6B, and FIG. 7. Note that the following description is based onthe assumption of an ideal situation for easy understanding and does notnecessarily reflect a real situation. Note also that the followingdescription is just a consideration and does not affect the validity ofthe invention.

FIG. 4 is a cross-sectional view of a transistor (thin film transistor)including an oxide semiconductor. An oxide semiconductor layer (OS) isprovided over a gate electrode (GE1) with a gate insulating layer (GI)interposed therebetween, and a source electrode (S) and a drainelectrode (D) are provided thereover. An insulating layer is provided soas to cover the source electrode (S) and the drain electrode (D).

FIG. 5 is an energy band diagram (schematic diagram) of the A-A′ sectionin FIG. 4. In FIG. 5, a black circle (●) and a white circle (◯)represent an electron and a hole and have electric charges (−q, +q),respectively. With a positive voltage (V_(D)>0) applied to the drainelectrode, the dashed line shows the case where no voltage is applied tothe gate electrode (V_(G)=0) and the solid line shows the case where apositive voltage is applied to the gate electrode (V_(G)>0). In the casewhere no voltage is applied to the gate electrode, carriers (electrons)are not injected to the oxide semiconductor side from an electrodebecause of high potential barrier, so that a current does not flow,which means an off state. On the other hand, when a positive voltage isapplied to the gate electrode, potential barrier is lowered, and thus acurrent flows, which means an on state.

FIGS. 6A and 6B are energy band diagrams (schematic diagrams) of theB-B′ section in FIG. 4. FIG. 6A illustrates an on state in which apositive voltage (V_(G)>0) is applied to the gate electrode (GE1) andcarriers (electrons) flow between the source electrode and the drainelectrode. FIG. 6B illustrates an off state in which a negative voltage(V_(G)<0) is applied to the gate electrode (GE1) and minority carriersdo not flow.

FIG. 7 illustrates the relationships between the vacuum level and thework function of a metal (ϕ_(M)) and between the vacuum level and theelectron affinity (χ) of an oxide semiconductor.

At normal temperature, electrons in the metal are degenerated and theFermi level is located in the conduction band. On the other hand, aconventional oxide semiconductor is an n-type semiconductor, in whichthe Fermi level (E_(F)) is away from the intrinsic Fermi level (E_(i))located in the middle of a band gap and is located closer to theconduction band. Note that it is known that part of hydrogen is a donorin an oxide semiconductor and is one factor causing an oxidesemiconductor to be an n-type semiconductor.

On the other hand, an oxide semiconductor according to one embodiment ofthe disclosed invention is an intrinsic (i-type) or a substantiallyintrinsic oxide semiconductor which is obtained by removing hydrogenthat is a factor for an n-type semiconductor from an oxide semiconductorand purifying the oxide semiconductor such that an element other than amain component of the oxide semiconductor (i.e., an impurity element) isprevented from being contained therein as much as possible. In otherwords, a feature is that a purified i-type (intrinsic) semiconductor, ora semiconductor close thereto, is obtained not by adding an impurityelement but by removing an impurity such as hydrogen or water as much aspossible. Thus, the Fermi level (E_(F)) can be comparable with theintrinsic Fermi level (E_(i)).

It is said that the band gap (E_(g)) of an oxide semiconductor is 3.15eV and the electron affinity (χ) is 4.3 V. The work function of titanium(Ti) included in the source electrode and the drain electrode issubstantially equal to the electron affinity (χ) of the oxidesemiconductor. In that case, a Schottky barrier for electrons is notformed at an interface between the metal and the oxide semiconductor.

At that time, the electron moves in the vicinity of the interfacebetween the gate insulating layer and the purified oxide semiconductor(the lowest portion of the oxide semiconductor which is stable in termsof energy) as illustrated in FIG. 6A.

In addition, as illustrated in FIG. 6B, when a negative potential isapplied to the gate electrode (GE1), the value of current is extremelyclose to zero because holes that are minority carriers are substantiallyzero.

In such a manner, an intrinsic (i-type) or substantially intrinsic oxidesemiconductor is obtained by being purified such that an element otherthan its main element (i.e., an impurity element) is contained as littleas possible. Thus, characteristics of the interface between the oxidesemiconductor and the gate insulating layer become obvious. For thatreason, the gate insulating layer needs to be able to form a favorableinterface with the oxide semiconductor. Specifically, it is preferableto use, for example, an insulating layer formed by a CVD method usinghigh-density plasma generated with a power supply frequency in the rangeof the VHF band to the microwave band, an insulating layer formed by asputtering method, or the like.

When the oxide semiconductor is purified and the interface between theoxide semiconductor and the gate insulating layer is made favorable, inthe case where the transistor has a channel width (W) of 1×10⁴ μm and achannel length (L) of 3 μm, for example, it is possible to realize anoff-state current of 10⁻¹³ A or less and a subthreshold swing (S value)of 0.1 V/dec (with a 100-nm-thick gate insulating layer).

The oxide semiconductor is purified as described above so as to containan element other than its main element (i.e., an impurity element) aslittle as possible, so that the thin film transistor can operate in afavorable manner.

<Resistance of Transistor Including Oxide Semiconductor to Hot CarrierDegradation>

Next, the resistance of a transistor including an oxide semiconductor tohot carrier degradation will be described with reference to FIGS. 8A and8B, FIGS. 9A and 9B, and FIGS. 10A and 10B. Note that the followingdescription is based on the assumption of an ideal situation for easyunderstanding and does not necessarily reflect a real situation. Notealso that the following description is just a consideration.

Main causes of hot carrier degradation are channel hot electroninjection (CHE injection) and drain avalanche hot carrier injection(DAHC injection). Note that only electrons are considered below forsimplicity.

CHE injection refers to a phenomenon in which electrons having gainedenergy higher than the barrier of a gate insulating layer in asemiconductor layer are injected into the gate insulating layer or thelike. Electrons gain energy by being accelerated by a low electricfield.

DAHC injection refers to a phenomenon in which electrons generated bycollision of electrons accelerated by a high electric field are injectedto a gate insulating layer or the like. A difference between DAHCinjection and CHE injection is whether or not they involve avalanchebreakdown caused by impact ionization. Note that DAHC injection requireselectrons having a kinetic energy higher than a band gap of asemiconductor.

FIGS. 8A and 8B illustrate energy required for each hot carrierinjection which is estimated from the band structure of silicon (Si),and FIGS. 9A and 9B illustrate energy required for each hot carrierinjection which is estimated from the band structure of anIn—Ga—Zn—O-based oxide semiconductor (IGZO). FIG. 8A and FIG. 9A showCHE injection and FIG. 8B and FIG. 9B show DAHC injection.

Regarding silicon, degradation caused by DAHC injection is more seriousthan that caused by CHE injection. This results from the fact thatcarriers (e.g., electrons) which are accelerated without colliding arevery few in silicon whereas silicon has a narrow band gap and avalanchebreakdown readily occurs therein. The avalanche breakdown increases thenumber of electrons capable of travelling over the barrier of the gateinsulating layer, and the probability of DAHC injection readily becomeshigher than that of CHE injection.

Regarding an In—Ga—Zn—O-based oxide semiconductor, the energy requiredfor CHE injection does not greatly differ from that in the case ofsilicon, and the probability of CHE injection is still low. In addition,the energy required for DAHC injection is substantially equal to theenergy required for CHE injection due to a wide band gap.

In other words, the probabilities of both CHE injection and DAHCinjection are low and the resistance to hot carrier degradation ishigher than that of silicon.

Meanwhile, the band gap of an In—Ga—Zn—O-based oxide semiconductor iscomparable to that of silicon carbide (SiC) which attracts attention asa material having a high withstand voltage. FIGS. 10A and 10B illustrateenergy required for each hot carrier injection regarding 4H—SiC. FIG.10A shows CHE injection and FIG. 10B shows DAHC injection. Regarding CHEinjection, an In—Ga—Zn—O-based oxide semiconductor has a slightly higherthreshold and can be said to have an advantage.

As described above, it can be seen that an In—Ga—Zn—O-based oxidesemiconductor has significantly higher resistance to hot carrierdegradation and higher resistance to source-drain breakdown thansilicon. It can also be said that a withstand voltage comparable to thatof silicon carbide can be obtained.

<Short-Channel Effect in Transistor Including Oxide Semiconductor>

Next, a short-channel effect in a transistor including an oxidesemiconductor will be described with reference to FIG. 11 and FIG. 12.Note that the following description is based on the assumption of anideal situation for easy understanding and does not necessarily reflecta real situation. Note also that the following description is just aconsideration.

The short-channel effect refers to degradation of electricalcharacteristics which becomes obvious with miniaturization of atransistor (a reduction in channel length (L)). The short-channel effectresults from the effect of a drain on a source. Specific examples of theshort-channel effect are a decrease in threshold voltage, an increase insubthreshold swing (S value), an increase in leakage current, and thelike.

Here, a structure capable of suppressing a short-channel effect isexamined by device simulation. Specifically, four kinds of models eachhaving a different carrier concentration and a different thickness of anoxide semiconductor layer were prepared, and the relationship between achannel length (L) and a threshold voltage (V_(th)) was checked. As themodels, bottom-gate transistors were employed, in each of which an oxidesemiconductor had a carrier concentration of 1.7×10⁻⁸/cm³ or1.0×10¹⁵/cm³ and an oxide semiconductor layer had a thickness of 1 μm or30 nm. Note that an In—Ga—Zn—O-based oxide semiconductor was used forthe oxide semiconductor layer, and a silicon oxynitride film with athickness of 100 nm was used as a gate insulating layer. It was assumedthat, in the oxide semiconductor, the band gap was 3.15 eV, the electronaffinity was 4.3 eV, the relative permittivity was 15, and the electronmobility was 10 cm²/Vs. The relative permittivity of the siliconoxynitride film was assumed to be 4.0. The calculation was performedusing device simulation software “ATLAS” produced by Silvaco Inc.

Note that there is no significant difference in calculation resultsbetween a top-gate transistor and a bottom-gate transistor.

FIG. 11 and FIG. 12 show calculation results. FIG. 11 shows the casewhere the carrier concentration is 1.7×10⁻⁸/cm³ and FIG. 12 shows thecase where the carrier concentration is 1.0×10¹⁵/cm³. FIG. 11 and FIG.12 each show the amount of change (ΔV_(th)) in threshold voltage(V_(th)) when a transistor whose channel length (L) is 10 μm is used asa reference and channel lengths (L) vary from 10 μm to 1 μm. As shown inFIG. 11, in the case where the carrier concentration in the oxidesemiconductor was 1.7×10⁻⁸/cm³ and the thickness of the oxidesemiconductor layer was 1 μm, the amount of change (ΔV_(th)) inthreshold voltage was −3.6 V. Moreover, as shown in FIG. 11, in the casewhere the carrier concentration in the oxide semiconductor was1.7×10⁻⁸/cm³ and the thickness of the oxide semiconductor layer was 30nm, the amount of change (ΔV_(th)) in threshold voltage was −0.2 V. Inaddition, as shown in FIG. 12, in the case where the carrierconcentration in the oxide semiconductor was 1.0×10¹⁵/cm³ and thethickness of the oxide semiconductor layer was 1 μm, the amount ofchange (ΔV_(th)) in threshold voltage was −3.6 V. Moreover, as shown inFIG. 12, in the case where the carrier concentration in the oxidesemiconductor was 1.0×10¹⁵/cm³ and the thickness of the oxidesemiconductor layer was 30 nm, the amount of change (ΔV_(th)) inthreshold voltage was −0.2 V. The results show that a short-channeleffect can be suppressed in a transistor including an oxidesemiconductor by a reduction in thickness of an oxide semiconductorlayer. For example, in the case where the channel length (L) isapproximately 1 μm, even with an oxide semiconductor layer havingsufficiently high carrier concentration, it can be understood that ashort-channel effect can be sufficiently suppressed when the thicknessof the oxide semiconductor layer is set to approximately 30 nm.

<Carrier Concentration>

A technical idea according to the disclosed invention is to make anoxide semiconductor layer as close as possible to an intrinsic (i-type)oxide semiconductor layer by sufficiently reducing the carrierconcentration thereof. A method for calculating the carrierconcentration and an actually measured carrier concentration will bedescribed with reference to FIG. 13 and FIG. 14.

First, a method for calculating the carrier concentration is brieflyexplained. The carrier concentration can be calculated in such a mannerthat a MOS capacitor is manufactured and the results of C—V measurement(C—V characteristics) of the MOS capacitor are evaluated.

Specifically, carrier concentration N_(d) can be calculated in thefollowing manner: C—V characteristics are obtained by plotting therelationship between the gate voltage V_(G) and capacitance C of a MOScapacitor; a graph of the relationship between the gate voltage V_(G)and (1/C)² is obtained from the C—V characteristics; a differentialvalue of (1/C)² in a weak inversion region of the graph is found; andthe differential value is substituted into Formula 1. Note that e, ε₀,and ε in Formula 1 represent elementary electric charge, vacuumpermittivity, and relative permittivity of an oxide semiconductor,respectively.

$\begin{matrix}{\left\lbrack {{Formula}\mspace{14mu} 1} \right\rbrack \mspace{619mu}} & \; \\{N_{d} = {{- \left( \frac{2}{e\; ɛ_{0}ɛ} \right)}/\frac{{d\left( {1/C} \right)}^{2}}{dV}}} & (1)\end{matrix}$

Next, carrier concentration actually measured by the above method isdescribed. A sample (a MOS capacitor) used for the measurement wasformed as follows: a titanium film was formed to a thickness of 300 nmover a glass substrate; a titanium nitride film was formed to athickness of 100 nm over the titanium film; an oxide semiconductor layerincluding an In—Ga—Zn—O-based oxide semiconductor was formed to athickness of 2 μm over the titanium nitride film; and a silver film wasformed to a thickness of 300 nm over the oxide semiconductor layer. Notethat the oxide semiconductor layer was formed using a target fordepositing an oxide semiconductor including In, Ga, and Zn(In:Ga:Zn=1:1:0.5 [atomic ratio]) by a sputtering method. Further, anatmosphere in which the oxide semiconductor layer was formed was a mixedatmosphere of argon and oxygen (with a flow ratio of Ar:O₂=30 (sccm): 15(sccm)).

FIG. 13 and FIG. 14 illustrate the C—V characteristics and therelationship between V_(G) and (1/C)², respectively. The carrierconcentration calculated using Formula 1 from the differential value of(1/C)² in a weak inversion region of the graph of FIG. 14 was6.0×10¹⁰/cm³.

In this manner, by using an i-type or substantially i-type oxidesemiconductor (for example, with a carrier concentration of less than1×10¹²/cm³, preferably less than or equal to 1×10¹¹/cm³), a transistorwith excellent off-state current characteristics can be obtained.

The structures, methods, and the like described in this embodiment canbe combined as appropriate with any of the structures, methods, and thelike described in other embodiments.

Embodiment 2

In this embodiment, examples of electronic devices each including thesemiconductor device according to any of the above-described embodimentswill be described with reference to FIGS. 15A to 15F. The semiconductordevice according to any of the above embodiments has unprecedentedexcellent characteristics. Therefore, an electronic device with a novelstructure can be provided by using the semiconductor device. Note thatthe semiconductor device according to any of the above embodiments isintegrated and mounted on a circuit board or the like, and incorporatedin an electronic device.

FIG. 15A illustrates a notebook personal computer including thesemiconductor device according to any of the above embodiments, andincludes a main body 301, a housing 302, a display portion 303, akeyboard 304, and the like. By applying the semiconductor deviceaccording to the disclosed invention to a personal computer, ahigh-performance personal computer can be provided.

FIG. 15B illustrates a personal digital assistant (PDA) including thesemiconductor device according to any of the above embodiments. A mainbody 311 is provided with a display portion 313, an external interface315, operation buttons 314, and the like. Further, a stylus 312 isprovided as an accessory for operation. By applying the semiconductordevice according to the disclosed invention to a personal digitalassistant (PDA), a high-performance personal digital assistant (PDA) canbe provided.

FIG. 15C illustrates an electronic book 320 as an example of electronicpaper including the semiconductor device according to any of the aboveembodiments. The electronic book 320 includes two housings, a housing321 and a housing 323. The housing 321 is combined with the housing 323by a hinge 337, so that the electronic book 320 can be opened and closedusing the hinge 337 as an axis. With such a structure, the electronicbook 320 can be used like a paper book.

The housing 321 includes a display portion 325, and the housing 323includes a display portion 327. The display portion 325 and the displayportion 327 can display a continuous image or different images. Astructure for displaying different images enables text to be displayedon the right display portion (the display portion 325 in FIG. 15C) andimages to be displayed on the left display portion (the display portion327 in FIG. 15C).

FIG. 15C illustrates an example in which the housing 321 is providedwith an operation portion and the like. For example, the housing 321 isprovided with a power switch 331, operation keys 333, a speaker 335, andthe like. The operation keys 333 allow pages to be turned. Note that akeyboard, a pointing device, or the like may also be provided on thesame side of the housing as the display portion. Furthermore, anexternal connection terminal (an earphone terminal, a USB terminal, aterminal that can be connected to an AC adapter and various cables suchas a USB cable, or the like), a recording medium insertion portion, andthe like may be provided on the back surface or the side surface of thehousing. The electronic book 320 can also serve as an electronicdictionary.

In addition, the electronic book 320 can send and receive informationwirelessly. Through wireless communication, desired book data or thelike can be purchased and downloaded from an electronic book server.

Note that electronic paper can be used for electronic devices in allfields as long as they can display data. For example, to display data,electronic paper can be applied to posters, advertisement in vehiclessuch as trains, a variety of cards such as credit cards, and the like aswell as electronic books. By applying the semiconductor device accordingto the disclosed invention to electronic paper, high-performanceelectronic paper can be provided.

FIG. 15D illustrates a cellular phone including the semiconductor deviceaccording to any of the above embodiments. The cellular phone includestwo housings, a housing 340 and a housing 341. The housing 341 includesa display panel 342, a speaker 343, a microphone 344, a pointing device346, a camera lens 347, an external connection terminal 348, and thelike. The housing 340 includes a solar cell 349 for charging thecellular phone, an external memory slot 350, and the like. An antenna isincorporated in the housing 341.

The display panel 342 has a touch panel function. A plurality ofoperation keys 345 displayed as images are indicated by dashed lines inFIG. 15D. Note that the cellular phone includes a booster circuit forincreasing a voltage output from the solar cell 349 to a voltage neededfor each circuit. It is possible for the cellular phone to have, inaddition to the above structure, a structure in which a noncontact ICchip, a small recording device, or the like are formed.

The display panel 342 changes the orientation of display as appropriatein accordance with the application mode. Further, the camera lens 347 isprovided on the same side as the display panel 342, so that the cellularphone can be used as a video phone. The speaker 343 and the microphone344 can be used for videophone calls, recording, and playing sound, etc.as well as voice calls. Moreover, the housings 340 and 341 in a statewhere they are developed as illustrated in FIG. 15D can be slid so thatone is lapped over the other. Therefore, the size of the cellular phonecan be reduced, which makes the cellular phone suitable for beingcarried around.

The external connection terminal 348 can be connected to an AC adapteror a variety of cables such as a USB cable, so that the cellular phonecan be charged or can perform data communication. Moreover, the cellularphone can store and transfer a larger amount of data by inserting arecording medium into the external memory slot 350. Further, in additionto the above functions, an infrared communication function, a televisionreception function, or the like may be provided. By applying thesemiconductor device according to the disclosed invention to a cellularphone, a high-performance cellular phone can be provided.

FIG. 15E illustrates a digital camera including the semiconductor deviceaccording to any of the above embodiments. The digital camera includes amain body 361, a display portion A 367, an eyepiece 363, an operationswitch 364, a display portion B 365, a battery 366, and the like. Byapplying the semiconductor device according to the disclosed inventionto a digital camera, a high-performance digital camera can be provided.

FIG. 15F illustrates a television set including the semiconductor deviceaccording to any of the above embodiments. In a television set 370, adisplay portion 373 is incorporated in a housing 371. Images can bedisplayed on the display portion 373. Here, the housing 371 is supportedby a stand 375.

The television set 370 can be operated with an operation switch includedin the housing 371 or by a remote controller 380. Channels and volumecan be controlled with a control key 379 included in the remotecontroller 380, and images displayed on the display portion 373 can thusbe controlled. Further, the remote controller 380 can be provided with adisplay portion 377 for displaying data to be output from the remotecontroller 380.

Note that the television set 370 preferably includes a receiver, amodem, and the like. The receiver allows the television set 370 toreceive a general television broadcast. In addition, the television set370 is capable of one-way (from a transmitter to a receiver) or two-way(between a transmitter and a receiver, between receivers, or the like)data communication when connected to a communication network by wired orwireless connection via the modem. By applying the semiconductor deviceaccording to the disclosed invention to a television set, ahigh-performance television set can be provided.

The structures, methods, and the like described in this embodiment canbe combined as appropriate with any of the structures, methods, and thelike described in other embodiments.

Example

In this example, oxidation of a conductive layer by high-density plasmatreatment according to an embodiment of the disclosed invention isconfirmed. The detailed description thereof is given below.

In this example, plasma was generated by excitation of a mixed gas ofoxygen and argon at a power supply frequency of 2.45 GHz under apressure of 500 Pa, and a conductive layer was treated using the plasma.The treatment was performed under three conditions where the lengths oftreatment time were 1 minute (60 seconds), 3 minutes (180 seconds), and10 minutes (600 seconds) to examine the relationship between treatmenttime and thickness of an oxide region.

Titanium films formed over glass substrates and aluminum films formedover glass substrates were separately prepared as conductive layers.Each of these films was subjected to the above plasma treatment at asubstrate temperature of 300° C. or 325° C. In other words, therelationship between treatment time and thickness of an oxide region wasexamined under four conditions: the titanium film at a substratetemperature of 300° C., the titanium film at a substrate temperature of325° C., the aluminum film at a substrate temperature of 300° C., andthe aluminum film at a substrate temperature of 325° C.

Examination results are shown in FIG. 16. It can be seen from FIG. 16that the oxidation rate of titanium is higher than that of aluminum. Inaddition, temperature dependence of the oxidation rate of titanium islarge, whereas temperature dependence of the oxidation rate of aluminumis small. Furthermore, it can be said that the thickness of an oxideregion of aluminum tends to be saturated in a short time.

Either of the materials can be provided with an oxide region with athickness (5 nm or more) sufficient to suppress short circuit between agate electrode and a source or drain electrode.

By performing oxidation treatment with high-density plasma as describedin this example, damage to an oxide semiconductor layer can be reducedand localized states due to oxygen deficiency can be reduced, ascompared to the case of performing oxidation treatment by normal plasmatreatment. In other words, characteristics of an oxide semiconductorlayer can be further improved.

In addition, by the above oxidation treatment, an oxide region is formedin part of a source or drain electrode (particularly, a portioncorresponding to a side surface thereof); therefore, short circuitbetween the gate electrode and the source or drain electrode can beprevented.

It can be understood from the above description that an embodiment ofthe disclosed invention is highly effective in improving reliability andother characteristics of a transistor including an oxide semiconductor.

This application is based on Japanese Patent Application serial no.2009-260368 filed with Japan Patent Office on Nov. 13, 2009, the entirecontents of which are hereby incorporated by reference.

1. (canceled)
 2. A semiconductor device comprising: an oxidesemiconductor layer; a first conductive layer comprising a regionoverlapping with the oxide semiconductor layer with an insulating filmtherebetween; a second conductive layer comprising a region overlappingwith the oxide semiconductor layer with a metal oxide layer havingconductivity; wherein the oxide semiconductor layer comprises indium,gallium and zinc, wherein the oxide semiconductor layer comprises acrystal having a grain size of 1 to 20 nm, wherein the second conductivelayer contains copper, wherein the metal oxide layer contains zinc, andwherein a side surface of the second conductive layer comprises anoxidized region.
 3. The semiconductor device according to claim 2,wherein the first conductive layer contains copper.
 4. A semiconductordevice comprising: an oxide semiconductor layer; a first conductivelayer comprising a region overlapping with the oxide semiconductor layerwith an insulating film therebetween; a second conductive layercomprising a region in contact with the oxide semiconductor layer;wherein the oxide semiconductor layer comprises indium, gallium andzinc, wherein the oxide semiconductor layer comprises a crystal having agrain size of 1 to 20 nm, wherein the second conductive layer comprisesa stacked structure including a first layer and a second layer, whereinthe first layer contains aluminum, chromium, copper, tantalum, titanium,molybdenum or tungsten, and wherein a side surface of the secondconductive layer comprises an oxidized region.
 5. The semiconductordevice according to claim 2, wherein the first conductive layer containscopper.
 6. A semiconductor device comprising: a transistor; a firstinsulating film over the transistor; and a second insulating film overthe transistor, wherein the transistor comprises: an oxide semiconductorlayer; a first conductive layer comprising a region overlapping with theoxide semiconductor layer with a third insulating film therebetween; anda second conductive layer comprising a region in contact with the oxidesemiconductor layer; wherein each of the first insulating film and thesecond insulating film comprises silicon oxide, silicon nitride oxide,silicon nitride, hafnium oxide, aluminum oxide or tantalum oxide,wherein the oxide semiconductor layer comprises indium, gallium andzinc, wherein the oxide semiconductor layer comprises a crystal having agrain size of 1 to 20 nm, wherein the first conductive layer containscopper, wherein the second conductive layer comprises a stackedstructure including a first layer and a second layer, wherein the firstlayer contains copper, and wherein a side surface of the secondconductive layer comprises an oxidized region.